Treated textile product



Patented Dec. 8, 1942 2,304,113 ICE TREATED TEXTILE PRODUCT Willard L. Morgan, Edgewood, and Earle Davis McLeod, Rumford, R. I., asslgnors to Arnold, Hoffman & Co. Incorporated, a corporation of Rhode Island No Drawing. Application August 3, 1940, Serial No. 351,199

22 Claims. (Cl. 8-142-5) This invention relates to textile materials which have been softened by treatment with new condensation products which softening treatment is resistant to washing and dry cleaning.

Many materials have been used as textile assistants for altering the softness, the easy wetting or the repellency of textile fibers, but each has been subject to some fault; thus, tallows, oils, and sulphonated oils have long been used in the fin shing of textiles for softening effects, but these effects are not permanent and are lost the first time the goods are washed. These materials also suffer from rancidity or objectionable odor development in the goods. Fatty alcohols have also been used as textile softeners, but these also wash out. Fatty amides and the quaternary salts of these, as well as fatty quaternaries produced from pyridine or the betaines, and fatty imidazoles, have been suggested astex tile modifying agents and in particular as textile softeners. While these materials are mostly fairly expensive and dark in color, these substances have shown the advantage of being somewhat resistant to washing. The quaternary salts of fatty acid condensations with aliphatic polyamines have also been used, particularly as these have shown a maximum resistance to washing up to this time. However, each of these types of materials has left considerable to be desired with regards to resistance to washing and as each of these materials has been unstable with respect to heat and oxidation, their use has been attended with the serious difllculty of the cloth being yellowed either by reason of the initially dark color of the product, or by its decomposition due to the heat used in drying the fabric. Furthermore, goods which have been finished with these materials have frequently during a few months storage become seriously yellow due to the softener being sensitive to oxidation.

It is an object of this invention to provide a new class of textile assistants such as wetting. softening, lubricating, and waterproofing agents having improved properties.

It is a further object to provide a process of softening textile materials of animal or vegetable origin with treatments which are resistant to heat and to oxidation and which permit the finishing and storage of the finished goods for long periods without any yellowing or without any odor development.

As further objects of our invention, we describe a process of treating textile materials with new condensation products which may be easily applied from aqueous solutions to give finishes on the cloth of a maximum softness, which effects are completely permanent to washing and to dry cleaning.

A still further object of our invention is to describe condensation products which are to lubricate either yarns or fabrics so as to make the mechanical flow of these in weaving or sewing proceed smoothly.

. The condensation products proposed for use in this invention are substituted ureas, thloureas. guanidines, biurets, guanyl ureas, or diguanidlnes of high molecular weight in which each of the terminal carbamyl nitrogens has been substituted through linkage with a polyamino acid amide.

These compounds are readily prepared by reacting the carbamyl derivatives, such as, urea, thioreau, guanidine salts, biuret, diguanidine, or guanyl urea with the condensationproducts secured from aliphatic polyamines and acids or acid esters or acid chlorides.

As suitable acids for condensing with the polyamines, we prefer those containing six or more carbons and preferably saturated aliphatic acids, such as, lauric, stearic, palm oil acids, although we may use the unsaturated or substituted fatty acids, such as rincinoleic, oleic, sebacic or chlorostearic, or mixtures of such fatty acids. These acids may be condensed with any of the aliphatic polyamines or substituted polyamines, such as, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexa methylene diamine, hydroxy ethyl ethylene diamine, ethyl ethylene diamine, 2,2,dimethyl-l,3,diamino propane, 1,3,diamino isoprcpanol, beta beta diamino diethyl ether, and beta beta diamino diethyl thioether.

The condensation products used in this invention are substituted ureas, thioureas, biurets, guanidines, diguanidines, or guanyl ureas of high molecular weight of the following general formula:

In this formula R1 corresponds preferably to a saturated aliphatic chain containing 6 or more carbons such as would result from the use of a saturated fatty acid or any of the other various types of acids already enumerated; thus, B: may also represent an unsaturated hydrocarbon, or R1 may carry other substituting groups such as hydroxyl, carboxyl, or chlorine. In each case the corresponding fatty acid, acid chloride, or ester may be used as a source to introduce this fatty radical into our condensation products as will be shown later. R6 is used to indicate hydrocarbon groups of similar type to R1 and in a given compound may be identical with R1 or be secured from a different fatty acid.

' In the formula Ra, Ra, R4, and Rs may represent either hydrogen, a simple alkyl of less than five carbons, or a similar hydroxy alkyl radical such asa beta ethanol group. R3 and R4 may also represent alternatively a second acid amide chain derived from an acid and a polyamine.

The chemical groups indicated by Di and D: may be oxygen in the case of the ureas, sulphur =8 with the thioureas, or imido (=N'H) with the guanidines. The letter g represents a small whole number ranging from .0 to 3 and while Di and D: may be the same as in the biurets they may be different as in the guanyl ureas.

Depending upon the nature of the aliphatic polyamine used in the condensation with the acids, the letter A is used to represent either a amino -(NH)-- group, a simple alkyl or alkylol substituted amino of less than five carbons, such as, (NC:H4OH) or (NC2H5) or oxygen, or sulphur. The figures f, a, e, l, m, and t represent small whole integers, f and 7 varying from lto6,eandlfrom0to6,andmandtfrom l to 6, and any of the hydrogens in the CH2 groups may be substituted by a simple alkyl or a hydroxy group.

The condensation products used in this invention are in many cases directly water soluble or water dispersible. In all cases the condensations are readily dissolved after treatment with acids, such as, acetic, lactic, boric, oxalic, benzoic, salicyclic, furoic, citric, tartaric, formic, phthalic, succinic, or alkyl naphthalene sulphonic acids or after reaction with an alkylating agent, such as, ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorohydrin, or dimethyl sulphate. The salts or alkylated products of our substituted urea condensates are indicated in the general formula given where B represents the acid hydrogen or alkyl groups and X the acid radical or halogen group, while for our primary urea. etc., condensations B and X disappear from the formula.

The condensation products which are applied to textiles in this invention are readily prepared by heating equimolal quantities of the acid and polyamine at temperatures from 130 to 200 degrees centigrade until the reaction is complete as shown by the loss of one molecule of water. The mix is then cooled back to 180 and one half me! or more of the urea or other carbamyl derivative added. Ammonia is rapidly liberated as the urea becomes substituted, the temperature being held between 170 and 200 C. The product may be cooled and used directly or at temperatures of 80 to 140, the various solubilizing acid or alkylating agents may be added in quantities of .2 to .5 mol. or more.

The linking by urea or other carbamyl compounds of two or more acid polyamine amide groups results in products of very large molecular weight which are found to show high substantivity to the various textile fibers, such as, cotton, viscose, cellulose acetate, linen, jute wool, "Nylon" and protein fibers and to give textile treatments which are permanent to washing and dry cleaning. This marked substantivity is found to arise from the presence of the urea or other similar carbamyl groups in such high molecular weight products. The urea group also increases the solubility in water which is very important since such large molecules which are desirable for substantivity are poorlysoluble. Thus our substituted ureas, although of double the molecular weight,

are more soluble than the acid polyamine amide condensations from which they are produced.

We have found that the sensitivencss to oxidation and to heat or light of the acid polyamine amide condensations and other proposed nitrogen containing textile ts which results in yellowing either in processing, drying, storage, or use of the treated fabrics is mainly caused by the presence of primary amino or NH: groups in the compounds and to a much lesser extent by secondary amino '(NH) groups. It is the primary amino group left in the acid polyamine amide condensations which is reacted upon by the urea or other carbamyl compound and removed during the formation of our substituted ureas, and we are thus able to secure compounds free of these difficulties which had checked technical use. Likewise, the urea and other carbamyl compounds will react with and eliminate secondary amino'groups and the yellowing arising from such groups and it is an alternative under this invention to use suilicient urea or other carbamyl compound to combine with all the primary and secondary amino groups in the acid polyamine amide, as well as merely the terminal groups as shown in the general formula already given. The resistance to scorching under heat is also found to be lowered to some degree by the use of unsaturated acids as the source of R1 and Re and while wemay use them in many types of application, for products of maximum resistance we prefer the use of the saturated fatty acids.

The invention will be further illustrated, but is not limited by the following examples in which the quantities are stated in parts by weight:

Example 1 To 9225 parts (2 mols.) or a polyalkyl amino acid amide of formula -melting at 58 0., soluble in water after treatment with benzyl chloride or an acid and of the following formula for the acetate salt:

O I CnHu--NH-CHaCHs-NHClhOHs-NH 0 cnnu-i t Nn-cmcm-mzomcnrmr 11 00,011: This product was somewhat heat sensitive, but by increasing the urea to 15.0 parts (2 mols.) in the above case a product was obtained which was very heat resistant, giving no yellowing under a hot ironing of treated cloth and in the following formula for the lactate salt:

l CHEN--NHCHIOhN-CHQCHPNH H OOsGHOHCHs (L bonate at 185 through a quetch containing a solution of 0.25 to 1% of the lactate salt, followed by a squeeze roll to remove excess liquid and then dried on a tenter frame in a hot air oven, the treated clothes acquired a very soft feel which was resistant to repeated washing and dry cleaning. 200 parts of lauric acid may be substituted in either of the above compositions for every 284 parts of stearic acid represented.

Example 2 Either of the Just described products as an aqueous solution of the acetate salt, containing only 2 to 6 pounds, dissolved in 1,200 gallons of water. was used to soak a cellulose acetate fabric for 30 minutes at 120 F., after which the cloth was hydroextracted in a. centrifuge and dried.

The treated cloth has a very soft feel and improved drape which is permanent.

Example 3 100 parts (2 mols.) of the condensate of stearlc acid and hydroxyethyl ethylene diamine of formula:

Ci1Hss- J-NHCHaCHs-NHCHsCHsOH is further condensed with 32.! parts (1 mol.) of guanidine carbonate by slowly adding the car- C. and raising the temperature to 190 C. The product obtained melted at 68-73 C., was soluble in water after adding acetic acid and applied to cotton cloth at a strength of 2 lbs. in 50 gallons; it gave a very soft handle which was resistant to washing and dry cleaning and the goods would not discolor or take on any odors either when heated, exposed tolight, or stored formonths. The formula of the product was:

cnnw- -Nncmcm-N-cmcmon =NH CnHu--NHCHaCHr-N-CHaCHsOH Example 4 8.1 parts (/2 mol) of urea are introduced into 100 parts of a polyalkyl amino acid amide made by condensing 284 parts of stearic acid and 104 parts hydroxyethyl ethylene diamine at a temperature of 160 C. with the following formula:

cl1nu -Nncnlcnmncmcmon at 185 C. and the temperature raised to 190 C.

The product obtained was a light yellow compound, soluble in water after treatment with acids and melting at 60-65 C. with a formula as follows:

0 cnnu- -nncmcxr-N-cmcmon I I CnHu&-NHCH:CH:NCH:CH:OH If the urea is increased to 16.2 parts (1 mol), a similar compound is obtained except that a biuret linkage is substituted for the oil, such as, olive oil Example 5 The Iauric acid condensate described'by the following formula;

and the salt formed with one molecule of acetic acid are soft, semiliquid water soluble, greasy materials which applied as aqueous solutions containing 2 to 10 lbs. in 50 gallons of water give yarns which are highly softened and lubricated and which operate through the usual spinning operations vary satisfactorily. I

Example 6 The products described in Example 5 are mixed with an equal amount of mineral oil or a vegetable which they readily emulsify in water and the mixture is applied at 2-10 lbs. in 50 gallons to yarns and fabric as a softener and lubricant.

Example 7 284 parts (1 mol) of stearic acid is mixed with parts (1 mol) of 1,3 diamino iso propanol and the mixture heated to C., at which point 1 mol of water is split out. The temperature is then raised to C. and 30 parts (/2 mol) of urea is slowly added and the batch raised to C., during which time /2 mol of ammonia is split off. The product obtained melts at 80-85 C., is

soluble after treatment with acetic acid andis heat resistant. The

acetate has the following formula:

This product when applied to fabric imparts in addition to a marked softening value, a lubricating value which permits easy passage of the needles in sewing machines. Applied to yarns it gives a soft lofty handle and lubricate these through the spinning and weaving operations.

Example 8 The acetate salt in the condensation product used in Example 7 is melted with an equal amount of Japan wax or carnauba wax and the melted mixture is then stirred into twice its weight of water. This mixture can then be readily mixed with further water to give solutions MB to 12 lbs.

in 50 gallons of water. Printed cotton cloth can y then be run into this mixture in a quetch followed by a squeeze roll and the cloth dried on dry cans. This gives a highly soft feeling cloth with a slight stiffness, most of which finish is resistant to washing.

Example 9 dibutyl orthohydroxy biphenyl disulphonic acid.

This paste may be used in the finishing of tex- 2 tiles which are normally difficult to wet, such as, a sulphur dyed cotton cloth. The cloth is immersed and treated in a solution of 2 to 10 lbs. of the mixture in 50 gallons of water. The dried saturated alkyl group, or like radicals which may carry other substituting groups, such as, hydroxyl, carboxyl, or chlorine, and in which Ra,

Ra, R4 and Rs may represent either hydrogen,

be mixed with cloth can be readily remoistened and is readily v absorbent so that it may be put through preshrinking or Sanforizing" operations very read- Example 10 Hard twisted acetate fabrics or other fabrics so constructed of yarns which are very highly and tightly twisted show very poor drape and are quite diflicult to soften. Very good softening and draping can be secured with these materials when they are treated in solutions of 1 to 10 lbs. of the lauric acid condensate described in Example 5.

Example 11 The hard twisted fabric, such as, a cellulose a simple alkyl of less than five carbons, or a similar hydroxyl alkyl radical and in which R: and R4 may further represent a second acid amide chain derived from an acid and a polyamine, and in which general formula the nature of the carbamyl groups is indicated by Di and D: which may be oxygen, sulphur, or imide groups, the number of such groups being as a ranges from 0 to 3; while in the side chains the letter A represents either amino (NH)-, a simple alkyl or alkylol substituted amino of less than five carbons, or oxygen, or sulphur, and the integers f and i vary from 1 to 6, while e and l vary from 0 to 6, and m and t from 1 to 6.

2. A textile material impregnated with the salt 0 of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

3. A textile material impregnated with a salt of a substituted carbamyl compound described by the general formula in claim 1 in which the fatty acid residues, R1 and Re, are derived from saturated fatty acids of six or more carbons.

4. A textile material impregnated and permanently softened with a salt of a substituted carbamyl compound described by the general formula in claim 1 in which the fatty acid residues R1 and Re, are derived from saturated fatty acids of six or more carbons.

5. A textile material impregnated with a substituted carbamyl compound of the following general formula in which the substituting groups are derived from the polyalkyl amino acid amides acetate alpaca is treated in a solution of 2 to 8 lbs. per 50 gallons of water of the acetate or other salts of the condensation products described in Example 4, mixed with an equal quantity of a hydroscopic agent, such as,.81ycerine, diethylene glycol, the monoethyl ether of diethylene glycol,

urea, hydroxy allwl substituted ureas or sugars. In each case the softener alone gives a very marked softening effect which is permanent and resistant to washing and dry cleaning and very much improves the draping qualities of these fabrics which, however, are further enhanced by the hydroscopic agents mixed therein.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is understood that we do'not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A textile material impregnated with a substituted carbamyl compound of the following formula: I v

, 0 Rs B: ne -h-ucrmrnrwm wherein R1 and Re represents similar or different hydrocarbon radicals of 6 or more carbons and may be either a saturated alwl group, an unsecured by reacting diethylene triamine and a saturated fatty acid of over six carbons as indicated by the letter n.

I C.Hmmy--N'HCHgCHsNHCHsCHz-IIIH o cmmi incmcnmncmcm-Nn C=Di in =Da l C-Hn-m-b-NHCHaCHr-N-CHrCHrOH '7. A textile material impregnated with the salt of a substituted carbamyl compound of the following formula, in which 1: indicates an radical:

acid

CnHir-iL;NHCHaCHa-N-CH:CH:OH

8. A textile material impregnated with the salt 9. A textile material impregnated with the salt of a substituted carbamyl compound of the following formula, in which X indicates an acid radical:

o la;

ClIHltA-NHCEC CHlCHINH with the substituted carbamyl compounds described by the general formula in claim 1.

12. A textile material impregnated with a mixture of a hydroscopic substance and a salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

13. A process of softening textile materials which comprises impregnating said textile materials with a substituted carbamyl compound as described by the general formula in claim 1.

14. A process of softening textile materials which comprises impregnating said textile materials with the salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

' 15. A process of softening textile materials which comprises impregnating said textile ma-,

terials with the salt of a substituted carbamyl compound of the following formula:

0 CuHn--NH-CHaCHr-N-CECEOH 16. A process of softening textile materials which comprises impregnating said textile materials with the salt of a substituted carbamyl compound of the following formula:

17. A process of softening textile materials which comprises impregnating said textile materialswith the salt of a substituted carbamyl compound of the following formula:

18. A process of softening textile materials which comprises impregnating the said textile materials with aqueous solutions or dispersions of a wetting agent and a salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

19. A process of softening textile materials which comprises impregnating the said textile materials with aqueous solutions of a hydroscopic agent and a salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1. V

20. A textile material impregnated with a reaction product of an alkylating substanceand a substituted carbamyl compound as described by the general formula in claim 1. 21. A textile material impregnated with a mixture of a material selected from the group consisting of mineral oils, vegetable oils and waxes and a salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

22. A process of softening textile materials which comprises impregnating the said textile materials with aqueous solutions or dispersions of a material selected from the group consisting of mineral oils, vegetable oils and waxes and a salt of an acid with the substituted carbamyl compounds described by the general formula in claim 1.

WILLARD L. MORGAN. EARLE DAVIS MOLEOD. 

